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EP1758940A1 - Procede pour produire des dispersions polymeres aqueuses - Google Patents

Procede pour produire des dispersions polymeres aqueuses

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Publication number
EP1758940A1
EP1758940A1 EP05750149A EP05750149A EP1758940A1 EP 1758940 A1 EP1758940 A1 EP 1758940A1 EP 05750149 A EP05750149 A EP 05750149A EP 05750149 A EP05750149 A EP 05750149A EP 1758940 A1 EP1758940 A1 EP 1758940A1
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EP
European Patent Office
Prior art keywords
monomer
weight
polymerization
total amount
radical initiator
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP05750149A
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German (de)
English (en)
Inventor
Reinhold J Leyrer
Dominik Winter
Marc Bothe
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BASF SE
Original Assignee
BASF SE
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Application filed by BASF SE filed Critical BASF SE
Publication of EP1758940A1 publication Critical patent/EP1758940A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation

Definitions

  • the present invention relates to a process for the preparation of an aqueous polymer dispersion by free-radically initiated aqueous emulsion polymerization of at least one ethylenically unsaturated monomer in the presence of at least one dispersant and at least one radical initiator at a polymerization temperature ⁇ 20 ° C., which is characterized in that a) in one Reaction vessel a1) at least a partial amount of deionized water, a2) at least a partial amount of the at least one radical initiator, a3) optionally a partial amount of the at least one dispersant and a4) optionally a partial or the total amount of one or more optional auxiliaries are introduced and brought to the polymerization temperature , then in a first stage b) the reaction vessel at polymerization temperature for a period of time T b1) a subset M of the at least one monomer, b2) optionally subme the at least one radical initiator, the at least one dispersant, the optional auxiliary agent
  • the present invention also relates to the aqueous polymer dispersions obtainable by the process according to the invention, the use thereof in various fields of application and the polymer powders obtainable from the aqueous polymer dispersions and their use in different fields of application.
  • the object of the present invention was to provide a new process for the preparation of aqueous polymer dispersions which ensures reliable reaction control of the free-radically initiated aqueous emulsion polymerization of ethylenically unsaturated monomers at temperatures ⁇ 20 ° C.
  • Another object was to provide aqueous polymer dispersions whose polymer films have increased mechanical stability and, at the same time, low stickiness.
  • Aqueous polymer dispersions are generally known. These are fluid systems which, as a disperse phase in an aqueous dispersion medium, contain polymer balls consisting of a plurality of intertwined polymer chains, the so-called polymer matrix or polymer particles, in disperse distribution.
  • the average diameter of the polymer particles is frequently in the range from 10 to 1000 nm, often 50 to 500 nm or 100 to 300 nm.
  • the polymer solids content of the aqueous polymer dispersions is generally 20 to 70% by weight.
  • Aqueous polymer dispersions are accessible in particular by radically initiated aqueous emulsion polymerization of ethylenically unsaturated monomers. This method has been described many times and is therefore well known to the person skilled in the art [cf. e.g. Encyclopedia of Polymer Science and Engineering, Vol. 8, pages 659 to 677, John Wiley & Sons, Inc., 1987; DC Blackley, Emulsion Polymerization, pages 155 to 465, Applied Science Publishers, Ltd., Essex, 1975; . DC Blackley, polymer latices, 2 nd Edition, Vol 1, pages 33 to 415, Chapman & Hall, 1997; H.
  • the free-radically initiated aqueous emulsion polymerization usually takes place in such a way that the ethylenically unsaturated monomers, generally with the use of dispersing aids such as emulsifiers and / or protective colloids, are dispersed in an aqueous medium and by means of at least one water-soluble free-radical polymerization initiator at polymerization temperatures> 50 ° C are polymerized. At polymerization temperatures ⁇ 20 ° C, however, the inventive method has proven to be advantageous.
  • Suitable at least one ethylenically unsaturated monomer for the radically initiated aqueous emulsion polymerization according to the invention are, in particular, free-radically polymerizable ethylenically unsaturated monomers, such as, for example, ethylene, vinylaromatic monomers, such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes, vinyl halides, such as vinyl chloride or vinylidene chloride, esters of vinyl alcohol and monocarboxylic acids having 1 to 18 carbon atoms, such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, esters of ⁇ , ⁇ -monoethylenically unsaturated mono preferably having 3 to 6 carbon atoms - And dicarboxylic acids, such as, in particular, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic
  • the monomers mentioned generally form the main monomers, which, based on the total amount of monomers, comprise a proportion of more than 50% by weight, preferably more than 80% by weight. As a rule, these monomers have only moderate to low solubility in water at normal conditions [20 ° C., 1 bar (absolute)].
  • Monomers which have an increased water solubility under the abovementioned conditions are those which have either at least one acid group and / or their corresponding anion or at least one amino, amido, ureido or N-heterocyclic group and / or protonated on nitrogen or contain alkylated ammonium derivatives.
  • Examples include ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids and their amides, such as e.g.
  • Acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, acrylamide and methacrylamide also vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid and their water-soluble salts as well as N-vinylpyrrolidone, 2-vinylpyhdin, 4-vinylpyridine, 2-vinylimidazole, 2 - (N, N-Dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-diethylamino) ethyl methacrylate, 2- (N-tert.
  • Monomers which usually increase the internal strength of the films of the polymer matrix normally have at least one epoxy, hydroxyl, N-methylol or carbonyl group, or at least two non-conjugated ethylenically unsaturated double bonds. Examples of these are two monomers having vinyl residues, two monomers having vinylidene residues and two monomers having alkenyl residues.
  • the di-esters of dihydric alcohols with ⁇ , ⁇ -monoethylenically unsaturated monocarboxylic acids are particularly advantageous, among which acrylic and methacrylic acid are preferred.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glycol diacrylate, 1, 2-propylene glycol diacrylate, 1,3-propylene glycol diacrylate, 1, 3-butylene glycol diacrylate and 1, 4, Propylene glycol dimethacrylate, 1, 3-propylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, 1, 4-butylene glycol dimethacrylate and divinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyla acrylate, diallyl maleate, diallyl fumaryl acrylate, trylene t-bis-acrylate, tri-acrylate, tri-acrylate, tri-acrylate, tri-acrylate, tri-acrylate, tri-ethoxylate,
  • the methacrylic acid and acrylic acid -CC 8 - hydroxyalkyl esters such as ethylene glycol diacrylate, 1, 2-propylene glycol diacrylate, 1,3-propylene glycol
  • esters of acrylic and / or methacrylic acid with alkanols and / or styrene having 1 to 12 carbon atoms or
  • those monomer mixtures can be used according to the invention which:
  • the free-radically initiated aqueous emulsion polymerization according to the invention gives polymers which are composed of the aforementioned monomers in copolymerized form. It is important that the monomers or monomer mixtures can also be polymerized in the step or gradient procedure known to the person skilled in the art by changing the monomer composition. It should also be noted at this point that in the context of this document the term monomer should also include monomer mixtures and the term polymer should also include copolymers.
  • At least one dispersant is used which keeps both the monomer droplets and the polymer particles formed during the polymerization dispersed in the aqueous phase and thus ensures the stability of the aqueous polymer dispersion produced.
  • Both protective colloids and emulsifiers can be considered as dispersants.
  • Suitable protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols, alkali metal salts of polyacrylic acids and polymethacrylic acids, cellulose, starch and gelatin derivatives or acrylic acid, methacrylic acid, maleic anhydride, 2-
  • Copolymers containing acrylamido-2-methylpropanesulfonic acid and / or 4-styrene sulfonic acid and their alkali metal salts but also N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide amine group-bearing acrylates, methacrylates, acrylamides and / or homo- and copolymers containing methacrylamides.
  • a detailed description of further suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pages 411 to 420.
  • emulsifiers and / or protective colloids can of course also be used. Often only emulsifiers are used as dispersants, the relative molecular weights of which, in contrast to the protective colloids, are usually below 1500. They can be of anionic, cationic or nonionic nature. Of course, in the case of the use of mixtures of surface-active substances, the individual components must be compatible with one another, which in the case of doubt can be checked by means of a few preliminary tests. In general, anionic emulsifiers are compatible with one another and with nonionic emulsifiers. The same applies to cationic emulsifiers, while anionic and cationic emulsifiers are usually not compatible with one another.
  • Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO grade: 3 to 50, alkyl radical: C 4 to C 12 ) and ethoxylated fatty alcohols (EO degree: 3 to 80; alkyl radical: C 8 to C) 36 ).
  • Lutensol ® A brands C 12 C 14 fatty alcohol ethoxylates, EO grade: 3 to 8
  • Lutensol ® AO brands C 13 C 15 - Oxo alcohol ethoxylates, EO grade: 3 to 30
  • Lutensol ® AT grades C 16 C 18 - fatty alcohol ethoxylates, EO grade: 11 to 80
  • Lutensol ® ON grades C 10 - oxo alcohol ethoxylates, EO grade: 3 to 11
  • Lutensol ® TO brands C 13 - oxo alcohol ethoxylates, EO grade: 3 to 20
  • Typical anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 to C 2 ), of sulfuric acid semiesters of ethoxylated alkanols (EO degree: 4 to 50, alkyl radical: C 12 to C 8 ) and ethoxylated alkyl phenols (EO Degree: 3 to 50, alkyl radical: C to C 12 ), of alkyl sulfonic acids (alkyl radical: C 12 to C ⁇ 8 ) and of alkylarylsulfonic acids (alkyl radical: C g to Cis).
  • alkyl sulfates alkyl radical: C 8 to C 2
  • sulfuric acid semiesters of ethoxylated alkanols EO degree: 4 to 50, alkyl radical: C 12 to C 8
  • ethoxylated alkyl phenols EO Degree: 3 to 50, alkyl radical: C to C
  • R 1 and R 2 are H atoms or C 4 - to C 24 -alkyl and are not simultaneously H atoms, and A and B can be alkali metal ions and / or ammonium ions.
  • R and R 2 are preferably linear or branched alkyl radicals having 6 to 18 carbon atoms, in particular having 6, 12 and 16 carbon atoms or -H, where R 1 and R 2 are not both H atoms at the same time
  • a and B are preferably sodium, potassium or ammonium, with sodium being particularly preferred.
  • Compounds I in which A and B are sodium, R 1 is a branched alkyl radical having 12 C atoms and R 2 is an H atom or R 1 are particularly advantageous.
  • Suitable cationic emulsifiers are generally a primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, and thiazolinium salts, which have a C 6 -C 1B alkyl, aralkyl or heterocyclic radical of amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts.
  • Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethylammonium) ethyl paraffinates, N-cetylpyridinium chloride, N-laurylpyridinium sulfate and N-cetyl-N, N, N-trimethylammonium bromide, N- Dodecyl- N, N, N-trimethylammonium bromide, N-octyl-N, N, N-trimethlyammonium bromide, N, N- Distearyl-N, N-dimethylammonium chloride and the Gemini surfactant N, N'- (lauryldimethyl) ethylenediamine dibromide.
  • nonionic and / or anionic emulsifiers are particularly suitable.
  • a total of 0.05 to 20 parts by weight, frequently 0.1 to 10 parts by weight and often 1 to 7 parts by weight of dispersant, based in each case on 100 parts by weight of aqueous polymerization medium, are formed from the total amounts of deionized water and the at least one dispersant used.
  • the total amount of the at least one dispersant can be placed in the reaction vessel before the addition of the at least one monomer is started. However, it is also possible to put only a portion of the at least one dispersant in the reaction vessel before the addition of the at least one monomer and to add the remaining amount during the polymerization. If necessary, however, the total amount of the at least one dispersant can also be added in the course of the polymerization. The total amount of at least one dispersant is often added in the course of the polymerization, in particular in the form of an aqueous monomer emulsion.
  • the total amount of deionized water is measured so that the polymer solids content of the aqueous polymer dispersion obtained according to the invention is 10 to 80% by weight, often 20 to 70% by weight and often 25 to 60% by weight, based in each case on the aqueous polymer dispersion.
  • the total amount of the deionized water can be placed in the reaction vessel before the addition of the at least one monomer is started. However, it is also possible to put only a subset of the deionized water in the reaction vessel before the addition of the at least one monomer and to add the remaining amount during the polymerization. Frequently ⁇ 75% by weight and often ⁇ 50% by weight or ⁇ 25% by weight of the total amount of deionized water are added in the course of the polymerization, in particular in the form of an aqueous monomer emulsion.
  • radical initiators are all those which are capable of initiating a radical aqueous emulsion polymerization at temperatures ⁇ 20 ° C. In principle, these can be both peroxides and azo compounds. Of course, redox initiator systems can also be used.
  • inorganic peroxides such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric acid, such as, for example, their mono- and disodium, potassium or ammonium salts or organic peroxides, such as alkyl hydroperoxides, for example tert-butyl, p-mentyl or cumyl hydroperoxide, and also Dialkyl or diaryl peroxides such as di-tert-butyl or di-cumyl peroxide can be used.
  • organic peroxides such as alkyl hydroperoxides, for example tert-butyl, p-mentyl or cumyl hydroperoxide, and also Dialkyl or diaryl peroxides such as di-tert-butyl or di-cumyl peroxide
  • the azo compound used is essentially 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (amidinopropyl) dihydrochloride (corresponds to V-50 from Wako Chemicals).
  • the aforementioned peroxides are essentially suitable as oxidizing agents for redox initiator systems.
  • Sulfur compounds with a low oxidation state such as alkali sulfites, for example potassium and / or sodium sulfite, alkali hydrogen sulfites, for example potassium and / or sodium hydrogen sulfite, alkali metal sulfites, for example potassium and / or sodium metabisulfite, formaldehyde sulfoxylates, for example potassium and / or Sodium formaldehyde sulfoxylate, alkali salts, especially potassium and / or sodium salts, aliphatic sulfinic acids and alkali metal hydrogen sulfides, such as, for example, potassium and / or sodium hydrogen sulfide, salts of polyvalent metals, such as iron (II) sulfate, iron (II) - Ammonium sulfate, iron (II) phosphate, endiols such as dihydroxymaleic acid, benzoin and / or ascorbic acid and reducing saccharides such
  • Redox initiator systems are preferably used in the process according to the invention.
  • the total amount of radical initiator is> 0.05 to ⁇ 6 parts by weight, often> 0.1 to ⁇ 4 parts by weight and often> 0.25 to ⁇ 3 parts by weight, in each case based on 100 Parts by weight of monomers used overall for the polymerization.
  • the total amount of the at least one radical initiator can be placed in the reaction vessel before the addition of the at least one monomer is started. However, it is also possible to put only a portion of the at least one radical initiator in the reaction vessel before the addition of the at least one monomer and to add the remaining amount during the polymerization.
  • > 30% by weight,> 60% by weight or> 90% by weight of the total amount of free radical initiators is initially introduced into the reaction vessel before the at least one monomer is added, and the remaining amount is added continuously in the course of the polymerization.
  • the half-life of the at least one radical initiator under polymerization conditions is 12 hours, ⁇ 8 hours or ⁇ 4 hours.
  • the quantitative ratios of oxidizing agent to reducing agent are familiar to the person skilled in the art. These are usually 5: 1 to 1: 5 or 3: 1 to 1: 3, often 2: 1 to 1: 2 or 1, 5: 1 to 1: 1.5 and often 1.3: 1 to 1 : 1.3 or 1.2: 1 to 1: 1.2. If the preferred redox initiator systems are used, the total amount of the oxidizing agent and / or the reducing agent can be introduced into the reaction vessel before the addition of the at least one monomer.
  • radical chain-transferring compounds for example, radical chain-transferring compounds, water-soluble organic solvents, polymer seeds, heavy metal compounds, water-soluble macromolecular host compounds which have a hydrophobic cavity and a hydrophilic shell, and biocides and defoamers are used as optional auxiliaries.
  • free-radical chain-transferring compounds are optionally used in order to reduce or to control the molecular weight of the polymers accessible by the polymerization.
  • Essentially aliphatic and / or araliphatic halogen compounds such as, for example, n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, tetrabromide, organic carbonyl, benzyl bromide, such as primary, secondary or tertiary aliphatic thiols, such as, for example, ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethiol, 2-methyl-2-propanethi
  • radical chain-transferring compounds examples include sulfur compounds described, as well as aliphatic and / or aromatic aldehydes such as acetaldehyde, Propionaldehyde and / or benzaldehyde, unsaturated saturated fatty acids, such as oleic acid or hydrocarbons with easily abstractable hydrogen atoms, such as toluene.
  • aliphatic and / or aromatic aldehydes such as acetaldehyde, Propionaldehyde and / or benzaldehyde
  • unsaturated saturated fatty acids such as oleic acid or hydrocarbons with easily abstractable hydrogen atoms, such as toluene.
  • the optionally used total amount of the radical chain transferring compounds is generally ⁇ 5% by weight, often ⁇ 3% by weight and often ⁇ 1% by weight. However, no radical chain-transferring compounds are preferred.
  • the total amount of the radical chain-transferring compounds can be placed in the reaction vessel before the addition of the at least one monomer is started, but it is also possible to put only a subset of the radical chain-transferring compounds in the reaction vessel before the addition of the at least one monomer and the remaining amount is added during the polymerization , If necessary, the total amount of radical chain transferring compounds can also be added in the course of the polymerization. The total amount of radical chain-transferring compounds is frequently added in the course of the polymerization.
  • Water-soluble organic solvents such as alcohols, for example methanol, ethanol, isopropanol, butanols, pentanols, glycols, such as, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol or dipropylene glycol, glycol ethers, such as, for example, monomethyl, monoethyl or monobutyl ether, can optionally also be used in the process according to the invention Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol or dipropylene glycol but also ketones, such as acetone, etc., can be used as a means of lowering the melting point of the aqueous polymerization medium.
  • alcohols for example methanol, ethanol, isopropanol, butanols, pentanols
  • glycols such as, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol or dipropylene
  • the amount of water-soluble organic solvent, based on the aqueous polymerization medium, formed from the total amounts of deionized water and the at least one dispersant, is ⁇ 50% by weight, often ⁇ 25% by weight, and often ⁇ 10% by weight , Especially at polymerization temperatures> - 5 ° C,> 0 ° C or> 5 ° C, no water-soluble organic solvent is generally used.
  • the total amount of water-soluble organic solvent can be placed in the reaction vessel before the at least one monomer is added. However, it is also possible to put only a partial amount of the water-soluble organic solvent in the reaction vessel before the addition of the at least one monomer and to add the remaining amount during the polymerization. If necessary, the total amount of solvent can also be added in the course of the polymerization. The total amount of water-soluble organic solvent is frequently placed in the reaction vessel before the at least one monomer is added.
  • the free-radically initiated aqueous emulsion polymerization can also be carried out in the presence of a polymer seed, for example in the presence of 0.01 to 3% by weight, frequently from 0.02 to 2% by weight and often from 0.04 to 1.5% by weight. -% of a polymer seed, based in each case on the total amount of monomers.
  • a polymer seed is used in particular when the particle size of the polymer particles to be produced by means of free-radical aqueous emulsion polymerization is to be set in a targeted manner (see, for example, US Pat. No. 2,520,959 and US Pat. No. 3,397,165).
  • polymer seed particles are used whose particle size distribution is narrow and whose weight-average diameter D w ⁇ 100 nm, frequently> 5 nm to ⁇ 50 nm and often> 15 nm to ⁇ 35 nm.
  • the determination of the weight-average particle diameter is known to the person skilled in the art and is carried out, for example, using the analytical ultracentrifuge method.
  • weight-average particle diameter is understood to mean the weight-average D w50 value determined by the analytical ultracentrifuge method (cf.
  • narrow particle size distribution is to be understood if the ratio of the weight-average particle diameter D w50 and the number-average particle diameter D N60 [D W5 o / D N5 o] ⁇ 2.0, preferably ⁇ 1, determined by the analytical ultracentrifuge method , 5 and particularly preferably 1, 2 or ⁇ 1.1.
  • the polymer seed is usually used in the form of an aqueous polymer dispersion.
  • the abovementioned quantitative data relate to the polymer solids content of the aqueous polymer seed dispersion; they are therefore given as parts by weight of polymer seed solids, based on the total amount of monomers.
  • foreign polymer seed is understood to mean a polymer seed which is in a was prepared separate reaction step and the monomeric composition of which is different from the polymer prepared by the free-radically initiated aqueous emulsion polymerization, but this means nothing other than that for the preparation of the Foreign polymer seeds and different monomers or monomer mixtures with different compositions are used to produce the aqueous polymer dispersion.
  • the preparation of a foreign polymer seed is familiar to the person skilled in the art and is usually carried out in such a way that a relatively small amount of monomers and a relatively large amount of emulsifiers are placed in a reaction vessel and a sufficient amount of polymerization initiator is added at the reaction temperature.
  • a foreign polymer seed with a glass transition temperature> 50 ° C., frequently> 60 ° C. or> 70 ° C. and often> 80 ° C. or> 90 ° C.
  • a polystyrene or a polymethyl methacrylate polymer seed is particularly preferred.
  • the total amount of foreign polymer seed can be placed in the reaction vessel before the at least one monomer is added. However, it is also possible to put only a portion of the foreign polymer seed in the reaction vessel before the addition of the at least one monomer and to add the remaining amount during the polymerization. If necessary, the total amount of polymer seed can also be added in the course of the polymerization.
  • the total amount of foreign polymer seed is preferably initially introduced into the reaction vessel before the at least one monomer is added.
  • the method according to the invention can optionally also be carried out in the presence of dissolved heavy metal ions, which can be present in changing valencies, such as iron, manganese, copper, chromium or vanadium ions.
  • Complexing agents for example ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA), are also frequently added, which complex the heavy metal ions and keep them in solution under the reaction conditions. Frequently ⁇ 0.1% by weight, ⁇ 0.05% by weight or ⁇ 0.025% by weight, based in each case on the total amount of monomers, of the aforementioned water-soluble heavy metal ions are used in the process according to the invention.
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • the total amount of heavy metal compounds providing heavy metal ions, often heavy metal ion complexes, can be placed in the reaction vessel before the addition of the at least one monomer is started. However, it is also possible to put only a subset of the heavy metal compounds in the reaction vessel before the addition of the at least one monomer and to add the remaining amount during the polymerization. If necessary, the total amount of heavy metal compounds can also be added in the course of the polymerization.
  • the total amount of heavy metal compounds is preferably initially introduced into the reaction vessel before the at least one monomer is added.
  • a water-soluble macromolecular host compound should be understood to mean host compounds which have a solubility of> 10 g / l of deionized water at the polymerization temperature and pressure. It is favorable if the solubility of the macromolecular host compounds is> 25 g / l,> 50 g / l or 100 g / l deionized water under the aforementioned conditions.
  • water-soluble macromolecular host compounds for example, calixarenes, cyclic oligosaccharides, noncyclic oligosaccharides and / or their derivatives can advantageously be used.
  • Calixarenes which can be used according to the invention are described in US Pat. No. 4,699,966, international patent application WO 89/08092 and Japanese patents 1988/197544 and 1989/007837.
  • cyclic oligosaccharides for example those described by Takai et al. Cycloinulohexose and heptose described in the Journal of Organic Chemistry, 1994, 59 (11), pages 2967 to 2975, but also cyclodextrins and / or their derivatives are used.
  • Particularly suitable cyclodextrins are ⁇ -cyclodextrin, ⁇ -cyclodextrin or v-cyclodextrin and their methyl, triacetyl, hydroxypropyl or hydroxyethyl derivatives.
  • Particularly preferred are the commercially available underivatized compounds, Cavamax ® W6, Cavamax ® W7 or Cavamax ® W8, the partially methylated compounds Cavasol ® W6M, Cavasol ® W7M or Cavasol ® W8M as well as the partially hydroxypropylated compounds Cavasol ® W6HP, Cavasol ® W7HP or Cavasol ® W8HP (trademarks of Wacker-Chemie GmbH).
  • Starches and / or their degradation products are used, for example, as noncyclic oligosaccharides.
  • the water-soluble starches or starch breakdown products are often native starches which have been made water-soluble by boiling with water, or starch breakdown products which are obtained from the native starches by hydrolysis, in particular by acid-catalyzed hydrolysis, enzymatically catalyzed hydrolysis or oxidation become.
  • Such degradation products are also known as dextrins, roasted dextrins or saccharified starches.
  • Their production from native starches is known to the person skilled in the art and is described, for example, in G. Tegge, Starch and Starch Derivatives, EAS Verlag, Hamburg 1984, pages 173ff. and pages 220ff. as well as in EP-A 0441 197.
  • starches of vegetable origin can be used as native starches, for example starches from corn, wheat, potatoes, tapioca, rice, sago and sorghum.
  • chemically modified starches or starch degradation products are also used.
  • Chemically modified starches or starch degradation products are understood to mean those starches or starch degradation products in which the OH groups are at least partially in a derivatized, for example in an etherified or esterified, form.
  • the chemical modification can be carried out on the native starches as well as on the degradation products. It is also possible to convert the chemically modified starches into their chemically modified breakdown products afterwards.
  • the esterification of starch or starch degradation products can be carried out using both inorganic and organic acids, their anhydrides or their chlorides.
  • Usual esterified starches are phosphated and / or acetylated starches or starch breakdown products.
  • the OH groups can be etherified, for example, with organic halogen compounds, epoxides or sulfates in aqueous alkaline solution.
  • suitable ethers are alkyl ethers, hydroxyalkyl ethers, carboxyalkyl ethers, allyl ethers and cationically modified ethers, for example (trisalkylammonium) alkyl ethers and (trisalkylammonium) hydroxyalkyl ethers.
  • the starches or the starch degradation products can be neutral, cationic, anionic or amphiphilic.
  • the production of modified starches and starch degradation products is the most professional (see. Ullmann's Encyclopedia of Industrial Chemischen mistry, 5 th ed., Vol. 25, pages 12 to 21 and references therein).
  • water-soluble starch degradation products and their chemically modified derivatives which can be obtained by hydrolysis, oxidation or enzymatic degradation of native starches or chemically modified starch derivatives, are used.
  • Such starch degradation products are also referred to as saccharified starches (cf. G. Tegge, starch and starch derivatives, EAS Verlag, Hamburg 1984, pages 220ff.).
  • Sugared starches and their derivatives are commercially available as such (e.g.
  • starch degradation products or chemically modified starch degradation products with a weight average molecular weight Mw im Range from 1000 to 30000 daltons and most preferably used in the range from 3000 to 10000 daltons.
  • Such starches are completely soluble in water at 25 ° C. and 1 bar, the solubility limit generally being above 50% by weight, which has proven to be particularly advantageous for the preparation of the copolymers according to the invention in an aqueous medium.
  • C * Pur ® 01906 M w approx. 20000
  • C * Pur ® 01934 M w approx. 3000
  • differential refractometer e.g. ERC 7511
  • Injection valve 20 ⁇ l valve: (e.g. VICI 6-way valve)
  • the amount of water-soluble macromolecular host compound optionally used in the present process according to the invention is generally 0.1 to 50% by weight, often 0.2 to 20% by weight and often 0.5 to 10% by weight, based in each case on the total amount of monomers.
  • the total amount of water-soluble macromolecular host compound can be placed in the reaction vessel before the addition of the at least one monomer is started. However, it is also possible to put only a partial amount of the water-soluble macromolecular host compound in the reaction vessel before the addition of the at least one monomer and to add the remaining amount during the polymerization. If desired, the total amount of water-soluble macromolecular host compound can also be added in the course of the polymerization. The total amount of water-soluble macromolecular host compound is preferably initially introduced into the reaction vessel before the at least one monomer is added.
  • the polymerization temperature is ⁇ 20 ° C, often ⁇ 15 ° C, ⁇ 10 ° C, ⁇ 5 ° C, ⁇ 0 ° C or ⁇ -5 ° C and often> -30 ° C,> -25 ° C,> -20 ° C,> -15 ° C,> -10 ° C,> -5 ° C or> 0 ° C.
  • the polymerization temperature is advantageously in the range> -30 ° C and ⁇ 15 ° C,> -20 ° C and ⁇ 10 ° C or> -10 ° C and ⁇ 10 ° C.
  • the reaction mixture is cooled by methods familiar to the person skilled in the art, for example by cooling using various cooling brines or liquid ammonia of the wall surfaces of the reaction vessel or separate cooling coils in the reaction vessel. It is favorable if the temperature difference between the polymerization temperature and the temperature of the cooling medium is> 10 ° C,> 20 ° C, 30 ° C,> 40 ° C or> 50 ° C. It is often advantageous if the temperature difference between the polymerization temperature and the temperature of the cooling medium is> 10 to ⁇ 60 ° C or> 20 to ⁇ 40 ° C.
  • a partial amount M of the at least one monomer and optionally partial amounts of the at least one radical initiator, the at least one dispersant, or the optional auxiliaries and / or deionized water are fed to the reaction vessel in a first stage at the polymerization temperature for a period of time T.
  • the time period T is advantageously> 1 minute and ⁇ 30 minutes,> 5 and ⁇ 20 minutes or> 5 and ⁇ 10 minutes and the subset M of the at least one monomer is 0.1 to 5% by weight, often 0.2 to 3 wt .-% and often 0.3 to 2 wt .-%, each based on the total amount of monomers.
  • the measures of the first stage are optionally repeated one or more times in corresponding subsequent stages, the subset of the at least one monomer being selected such that the subset Mn + 1 of the subsequent stage n + 1 is greater than the subset Mn of the previous stage n, the quotient of the time period Tn + 1 of the subsequent step n + 1 and the time period Tn of the previous step n> 0.5 and ⁇ 2 and the total amount of all monomer subsets ⁇ 30% by weight, based on the total amount of monomers.
  • the subset of the at least one monomer is selected such that the subset Mn + 1 of the subsequent stage n + 1 is greater than the subset Mn of the previous stage n.
  • the monomer subset Mn + 1 of the subsequent stage is advantageously Stage n + 1 by 10 to 300% by weight, frequently by 20 to 200% by weight and often 50 to 100% by weight above the monomer subset Mn of the previous stage n.
  • the total amount of all monomer subsets is ⁇ 30% by weight. %, often ⁇ 20 wt .-% and often ⁇ 10 wt .-%, each based on the total amount of monomers. It is also important that the quotient of the time period Tn + the subsequent stage n + 1 and the time period Tn of the previous stage n> 0.5 and ⁇ 2, often> 0.7 and ⁇ 1.3 or> 0.9 and ⁇ 1, 1 and in particular 1.
  • the monomer subset of the first or the subsequent stages can the Re-. Action vessel are fed at once ("weft"), discontinuously or continuously.
  • the respective partial monomer quantity is added continuously with a constant monomer quantity flow within the respective time period T, the monomer quantity flow increasing from stage to stage in accordance with the increase in the monomer partial quantity
  • the polymerization conditions type and amount of free radical initiator, polymerization temperature, type and amount of dispersant etc.
  • the monomer partial amounts are> 70% by weight, preferably> 80 % By weight and particularly preferably> 90% by weight, based in each case on the respective partial monomer quantity, have been converted by polymerization, which can be verified in a simple manner using calorimetric measurements.
  • reaction vessel immediately after the addition of the partial monomer at polymerization temperature during a period of time TP the remaining amount of the at least one monomer, the remaining amounts of the at least one radical initiator, the at least one dispersant, or the optional auxiliaries and / or or added to deionized water and the reaction mixture is then left at the polymerization temperature until the total amount of at least one monomer is converted to> 90% by weight, often> 95% by weight and often> 98% by weight is.
  • the remaining amount of the at least one monomer can be fed to the reaction vessel discontinuously or continuously within the time period TP, often continuously with a constant flow rate.
  • the time period TP is usually> 1 hour and ⁇ 10 hours, often> 2 and ⁇ 8 hours and often> 3 and ⁇ 6 hours.
  • the polymerization conditions type and amount of free radical initiator, polymerization temperature, type and amount of dispersant, etc.
  • the polymerization conditions are selected so that at least one monomer at the end of the time period TP is> 70% by weight, preferably> 80% by weight and particularly preferably> 90% by weight or> 95% by weight, in each case based on the total amount of monomers, is reacted by polymerization.
  • the feeds mentioned in stages b) to d) are cooled and fed to the reaction vessel, often at a temperature which is equal to or lower than the polymerization temperature.
  • the temperature of the feeds is advantageously lower than the polymerization temperature, as a result of which part of the the polymerization energy can be used to heat the feeds to the polymerization temperature, as a result of which the cooling surfaces in or on the reaction vessel are dimensioned to be smaller, or the amounts of feeds increased over time, and the overall cycle times can thus be reduced.
  • the cooling of the reaction vessel is interrupted after the total amount of monomers has been fed in after the period of time TP, as a result of which the polymerization energy which may still be released heat up the reaction mixture and to complete the monomer conversion to> 80% by weight,> 90 % By weight or> 95% by weight, based in each case on the total amount of monomers.
  • the composition of the monomers used for example the partial amount (s) during the time period (s) T or the remaining amount during the time period TP, can be changed discontinuously, stepwise or continuously in the course of the process according to the invention, whereby two - or multiphase polymer particles or polymer particles with gradient morphology can be formed.
  • the process according to the invention can be carried out at a pressure of less than, equal to or greater than 1 bar (absolute).
  • the pressure can be 1.2, 1.5, 2, 5, 10, 15 bar or even higher. If emulsion polymerizations are carried out under reduced pressure, pressures of ⁇ 950 mbar, often of ⁇ 900 mbar and often ⁇ 850 mbar (absolute) are set.
  • the free radical aqueous emulsion polymerization is advantageously carried out under an inert gas atmosphere, such as, for example, under nitrogen or argon at atmospheric pressure.
  • aqueous polymer dispersions whose polymers have a glass transition temperature or a melting point in the range from -60 to 270 ° C.
  • the glass transition temperature is often> -50 to ⁇ 100 ° C or> -40 to ⁇ 50 ° C.
  • the glass transition temperature T g means the limit value of the glass transition temperature which, according to G. Kanig (Kolloid-Zeitschrift & Zeitschrift fur Polymer, Vol. 190, p. 1, equation 1), strives with increasing molecular weight.
  • the glass transition temperature or melting point is determined by the DSC method (differential scanning calorimetry, 20 K / min, midpoint measurement, DIN 53765).
  • T ⁇ x 1 / T ⁇ 1 + xW + .... x T, g>
  • x 1 , x 2 , .... x ⁇ are the mass fractions of the monomers 1, 2, .... n
  • T g 1 , T g 2 , .... T g n are the glass transition temperatures of only one of the Monomers 1, 2, .... n built up polymers in degrees Kelvin.
  • the T g values for the homopolymers of most monomers are known and are listed, for example, in Ullmann's Ecyclopedia of Industrial Chemistry, Vol. 5, Vol. A21, page 169, VCH Weinheim, 1992; further sources for glass transition temperatures of homopolymers are, for example, J.
  • the aqueous polymer dispersions obtainable by the process according to the invention often have polymers whose minimum film-forming temperature MFT ⁇ 80 ° C. is frequently ⁇ 50 ° C. or ⁇ 30 ° C. Since the MFT is no longer measurable below 0 ° C, the lower limit of the MFT can only be specified by the T g values.
  • the MFT is determined in accordance with DIN 53787.
  • the aqueous polymer dispersion obtained usually has a polymer solids content of> 10 and ⁇ 80% by weight, frequently> 20 and ⁇ 70% by weight and often> 25 and ⁇ 60% by weight, in each case based on the aqueous polymer dispersion.
  • the number-average particle diameter (cumulant z-average) determined using quasi-elastic light scattering (ISO standard 13 321) is generally between 10 and 2000 nm, often between 20 and 1000 nm and often between 100 and 700 nm or 100 to 400 nm.
  • the polymers obtainable by the process according to the invention often have a higher molecular weight than the polymers accessible at temperatures> 20 ° C. and at the same time a lower degree of crosslinking.
  • the polymers accessible by the process according to the invention with a glass transition temperature ⁇ 20 ° C. after filming have a significantly lower tack ("tack") than the polymers obtained at higher polymerization temperatures.
  • aqueous polymer dispersions obtained according to the invention are frequently stable over several weeks or months and usually show practically no phase separation, deposition or coagulum formation. They are particularly suitable as binders in adhesives, sealants, plastic plasters, paper coating slips and paints, for finishing leather and textiles, for fiber binding and for modifying mineral binders.
  • the aqueous polymer dispersions obtainable according to the invention can be easily dried into redispersible polymer powders (e.g. freeze drying or spray drying). This is especially true if the glass transition temperature of the polymer contained in the aqueous polymer dispersion is> 50 ° C, often> 60 ° C or> 70 ° C, often> 80 ° C or> 90 ° C or> 100 ° C.
  • the polymer powders are also suitable as binders in adhesives, sealants, plastic plasters, paper coating slips and paints, for finishing leather and textiles, for fiber binding and in particular for modifying mineral binders.
  • the polymer films or polymers present in powder form that are accessible from the aqueous polymer dispersions according to the invention can have ordered areas, in particular iso- and syndiotactic areas, if a monomer mixture is used for the polymerization which is> 10 wt. -%,> 50 wt .-%,> 80 wt .-% or even 100 wt .-% prochiral ethylenically unsaturated monomers.
  • the ordered, often partially crystalline areas differ from the disordered areas in their phase transition temperatures. In differential thermal analysis or in dielectric spectroscopy, the polymers according to the invention frequently have at least two phase transition temperatures.
  • This can be, for example, two glass transition temperatures or at least one glass transition temperature and one melting point.
  • the presence of at least two transition temperatures in a polymer opens up a way of producing new thermoplastic elastomers which are of economic interest and which have hitherto been inaccessible via the free-radically initiated aqueous emulsion polymerization.
  • the inventive method ensured in the free-radically initiated aqueous emulsion polymerization at temperatures of ⁇ 20 C C safe driving by which a concentration of monomers and their sudden Abresure can be reliably avoided, as well as short and therefore economic polymerization, which is comparable to or shorter than the at> 50 ° C usually achievable polymerization times.
  • the solids contents were generally determined by drying a defined amount of the aqueous polymer dispersion (approx. 5 g) at 140 ° C. in a drying cabinet to constant weight. Two separate measurements were carried out in each case. The value given in the respective examples represents the average of the two measurement results.
  • the average particle diameter of the copolymer particles was generally determined by dynamic light scattering on a 0.005 to 0.01 percent by weight aqueous dispersion at 23 ° C. using an Autosizer IIC from Malvern Instruments, England. The average diameter of the cumulant evaluation (cumulant z-average) of the measured autocorrelation function is given (ISO standard 13321).
  • Feed 1 was then metered in uniformly over 6.5 hours, the internal temperature always being kept at 0.degree.
  • feed 2 was started, 0.5% by weight of feed 2 being present within the first 10 minutes, immediately thereafter within the next 10 minutes 1.0% by weight of feed 2, directly thereafter within 1.5% by weight of feed 2 over the next 10 minutes and directly thereafter the rest of feed 2 were metered in uniformly over the course of 5.5 hours.
  • Feed 1 consisted of 112.5 g of a 5% strength by weight aqueous solution of sodium disulfite.
  • Feed 2 was an aqueous emulsion prepared from 71.0 g of deionized water, 5.0 g of acrylic acid, 245.0 g of n-butyl acrylate and 12.5 g of a 15% by weight aqueous solution of sodium lauryl sulfate.
  • reaction mixture was stirred for a further 15 minutes at 0 ° C. and then warmed to room temperature (20 to 25 ° C.).
  • the aqueous polymer dispersion obtained had a solids content of 26% by weight.
  • the average particle size was 320 nm.
  • Example 1 was repeated with the difference that the polymerization temperature was 50 ° C.
  • the aqueous polymer dispersion obtained had a solids content of 26% by weight.
  • the average particle size was 200 nm.
  • Feed 1 was then metered in uniformly over 4.5 hours, the internal temperature being kept at 0.degree.
  • feed 2 was started, with 0.5% by weight of feed 2 within the first 10 minutes, immediately thereafter within the next 10 minutes 1.0% by weight of feed 2, directly thereafter within 1.5% by weight of feed 2 over the next 10 minutes, then 2.5% by weight of feed 2 directly thereafter within the next 10 minutes, then 3.5% by weight of feed 2 immediately afterwards within the next 10 minutes
  • Feed 2 and then the rest of feed 2 were then metered in uniformly within 3 hours and 10 minutes.
  • Feed 1 consisted of 8 g of a 5% strength by weight aqueous solution of sodium disulfite.
  • Feed 2 was an aqueous emulsion made from
  • reaction mixture was stirred at 0 ° C. for a further 15 minutes and then warmed to room temperature.
  • the aqueous polymer dispersion obtained had a solids content of 40% by weight.
  • the mean particle size was 205 nm.
  • Example 2 was repeated with the difference that feed 2 should be metered in uniformly within 4 hours. Approximately A sudden temperature surge was observed 2 hours after the start of feed 2, at which the internal temperature of the reaction vessel could no longer be controlled (internal temperature rose by 12 ° C. at maximum external cooling output). The attempt was canceled.
  • Feed 1 was then metered in uniformly over 6.5 hours, the internal temperature being kept at 0.degree. At the same time starting with feed 1, feed 2 was started, 0.5% by weight of feed 2 being connected within the first 10 minutes, immediately afterwards within the next 10 minutes 1.0% by weight of feed 2, directly connecting to it within the next 10 minutes 1.5 wt .-% of feed 2 and immediately thereafter the rest of feed 2 were evenly metered in over 5.5 hours.
  • Feed 1 consisted of 112.5 g of a 5% strength by weight aqueous solution of sodium disulfite.
  • Feed 2 was an aqueous emulsion made from
  • reaction mixture was stirred at 0 ° C. for a further 15 minutes and then warmed to room temperature.
  • the aqueous polymer dispersion obtained had a solids content of 26% by weight.
  • the average particle size was 370 nm.
  • aqueous dispersions of Examples 1 and 3 and Comparative Example 1 were poured into a rectangular silicone mold measuring 7.5 ⁇ 16 cm and dried for one week at room temperature. The amount of aqueous polymer dispersion was measured such that a polymer film with a layer thickness of 2 +/- 0.2 mm was formed in each case. Clear films were obtained. Shoulder rods with dimensions S2 described there were produced from the dried films as test specimens in accordance with DIN 53 504. Due to the highly viscous-fluid behavior of the film, no suitable test specimen could be obtained from the dispersion of comparative example 1.

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Abstract

L'invention concerne un procédé pour produire une dispersion polymère aqueuse au moyen d'une polymérisation d'émulsion aqueuse initiée radicalement d'au moins un monomère non saturé en éthylène en présence d'au moins un agent dispersant et d'au moins un initiateur de radicaux à une température de polymérisation inférieure ou égale à 20°C.
EP05750149A 2004-06-14 2005-06-09 Procede pour produire des dispersions polymeres aqueuses Withdrawn EP1758940A1 (fr)

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DE102004028391A DE102004028391A1 (de) 2004-06-14 2004-06-14 Verfahren zur Herstellung wässriger Polymerisatdispersionen
PCT/EP2005/006199 WO2005121188A1 (fr) 2004-06-14 2005-06-09 Procede pour produire des dispersions polymeres aqueuses

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DE102006050336A1 (de) * 2006-10-25 2008-05-08 Wacker Polymer Systems Gmbh & Co. Kg Geminitensid enthaltende Dispersionspulverzusammensetzungen
US8529694B2 (en) * 2006-10-26 2013-09-10 Air Products And Chemicals, Inc. Powdered acetylenic surfactants and compositions containing them
FI20086122L (fi) * 2008-11-24 2010-05-25 Kemira Oyj Polymeerikoostumus
CA2784024C (fr) * 2009-12-16 2018-03-13 Yvon Durant Polymerisation en emulsion d'esters d'acide itaconique
US10738139B2 (en) 2018-12-18 2020-08-11 Itaconix Corporation Decarboxylation and amidation of polyitaconic acid polymers

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US3560454A (en) * 1967-12-20 1971-02-02 Dynamit Nobel Ag Process for the continuous polymerization and copolymerization of ethylenically unsaturated compounds
DE3905010A1 (de) * 1989-02-18 1990-08-23 Basf Ag Waessrige kunstharzdispersionen
DE4141760A1 (de) * 1991-12-18 1993-06-24 Basf Ag Waessrige polymerisatdispersion
EP0661302B1 (fr) * 1993-12-23 1999-09-01 Nitto Denko Corporation Procédé de préparation d'une dispersion aqueuse d'un polymère acrylique, le polymère acrylique ainsi obtenu et composition adhésive sensible à la pression contenant ce polymère acrylique
DE19545096A1 (de) * 1995-12-04 1997-06-05 Basf Ag Verfahren zur Herstellung einer wäßrigen Polymerisatdispersion
DE19805122A1 (de) * 1998-02-09 1999-04-22 Basf Ag Verfahren zur Herstellung wässriger Polymerisatdispersionen mit geringem Restmonomerengehalt
DE19825486C2 (de) * 1998-06-08 2000-07-06 Stockhausen Chem Fab Gmbh Wasserabsorbierende Polymere mit supramolekularen Hohlraummolekülen, Verfahren zu deren Herstellung und deren Verwendung
DE19939325A1 (de) * 1999-08-19 2001-02-22 Basf Ag Verfahren zur Herstellung wässriger Polymerdispersionen
DE10063160A1 (de) * 2000-12-18 2002-06-20 Basf Ag Wässrige Polymerisatdispersion enthaltend Kautschukteilchen und verstärkend wirkende Polymerisatteilchen

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